3-alkenoxyoxetanes



United States Patent 3,446,819 3-ALKENOXYOXETANES Alan E. Ardis, North Haven, and John A. Wojtowicz,

East Haven, Conn., assignors to Olin Mathieson Chemical Corporation, a corporation of Virginia No Drawing. Filed June 14, 1966, Ser. No. 557,377

Int. Cl. C07d 3/00; C07f 9/08; C08k 1/60 US. Cl. 260-333 2 Claims ABSTRACT OF THE DISCLOSURE Alkenoxyoxetanes are prepared by isomerizing an allyloxyoxetane compound in the presence of a catalyst, such as potassium t-butoxide, lithium hydroxide, etc. In turn, the alkenoxyoxetanes can be hypochlorinated to yield the corresponding hydroxyoxetanes. The hydroxyoxetanes on reaction with organic phosphites yield oxetane ring-containing phosphites useful as stabilizers for halogen-containing resins.

wherein R and R are each selected from the group consisting of hydrogen and alkyl of from 1 to inclusive carbon atoms.

Hydroxyoxetanes of this invention have the formula:

rv-p cn om R OH wherein R and R are each selected from the group consisting of hydrogen and alkyl of from 1 to 5 inclusive carbon atoms.

Preparation of alkenoxyoxetanes In preparing the novel alkenoxyoxetanes of this invention an allyloxyoxetane compound of the formula:

wherein R and R are each selected from the group consisting of hydrogen and alkyl of from 1 to 5 inclusive carbon atoms, is isomerized in the presence of a suitable catalyst at a temperature of from about 0 to about 100 C. to yield the corresponding alkenoxyoxetane.

Allyloxyoxetane compounds useful in preparing the novel alkenoxyoxetane compounds of this invention include 3-allyloxyoxetane, 3(3'-methy1) allyloxyoxetane,

3(3',3' dimethyl) allyloxyoxetane, 3(3 methyl 3'- ethyl) allyloxyoxetane, 3(3' ethyl 3 propyl) allyloxyoxetane, 3(3, 3- dipropyl)allyloxyoxetane, 3(3'- methyl 3 isopropyl) allyloxyoxetane, 3(3' ethyl 3'- isopropyl) allyloxyoxetane, 3=(3,3' dibutyl) allyloxyoxetane, 3(3 methyl 3 isobutyl) allyloxyoxetane, 3 (3' ethyl 3' isobutyl) allyloxyoxetane, 3'(3' methyl 3 amyl) allyloxyoxetane, 3(3 isopropyl 3'- amyl) allyloxyoxetane, 3(3' butyl 3 isoamyl) allyloxyoxetane, 3(3',3'-diisoamyl) allyloxyoxetane, etc. Preferably, the isomerization reaction is carried out in the presence of an inert organic solvent. The useful solvents include hexamethylphosphoramide dimethylsulfoxide, 1,2-dimeth0xyethane, dimethylformamide, dimethylacetamide, tetrahydrofuran, sulfolane, etc. A wide variety of catalysts can be employed in elfecting the isomerization reaction. Suitable basic catalysts include potassium tbutoxide, sodium hydroxide, potassium hydroxide, sodium t-butoxide, lithium t-butoxide, lithium hydroxide, etc.

After filtration 0f the reaction mixture to remove any insoluble materials which may have formed during the isomerization reaction the alkenoxyoxetane product can be recovered by any of a variety of methods known in the art, such as by distillation, extraction, etc.

Thes starting allyloxyoxetane compounds can be obtained in the manner described in Polak et al. application Ser. No. 399,852, filed Sept. 28, 1964 and now abandoned. For example, allyloxyoxetane, which has the formula:

(5H2CH=CH1 can be prepared by first reacting allyl alcohol with gaseous chlorine at a temperature below 50 C. to yield a reaction mixture containing 2-allyloxy-3-chloro-l-propanol which, in turn, is dehydrohalogenated in the presence of aqueous sodium hydroxide at a temperature below C. to yield allyloxyoxetane.

Preparation of Hydroxyoxetanes According to the process of this invention hydroxyoxetane compounds can be prepared by hypochlorinating the novel alkenoxyoxetanes of the formula:

wherein R and R have the same meaning as previously described. The reaction is conveniently carried out by passing gaseous chlorine into a solution of the alkenoxyoxetane, for example, propenoxyoxetane in a water-acetone or water-dioxane mixture. If desired, the reaction can be conducted by adding liquid chlorine to the alkenoxyoxetane dissolved in a suitable solvent. Usually about 1 mole of chlorine is utilized per mole of the starting alkenoxyoxetane.

Generally the hypochlorination reaction is conducted at a temperature of from about 20 to +50 C. and preferably, at a temperature of from about 0 to +25 C. In order to achieve high yields it is necessary to employ a hydrogen chloride acceptor in the reaction mixture. Useful hydrogen chloride acceptors include calcium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, lime, etc. The stoichiometric requirement of the acid acceptor can be employed although an excess of up to 200 percent or more may be used, if desired.

Starting alkenoxyoxetanes useful in preparing hydroxy- 4 pure S-hydroxyoxetane, a colorless liquid, B.P. 72 C. at 10 mm. Hg, 21 1.4335, (i 1.125, having the formula:

oxetanes by the novel process of this invention include 3- n-propenoxyoxetane, 3-n-butenoxyoxetane, 3-isobutenoxy- 5 CHFCHTCH oxetane, 3-n-amylenoxyoxetane, 3 n heptenoxyoxetane, H etc. Analysis.-Calcd for C H O C, 48.64; H, 8.16.

EXAMPLE I Found: C, 47.8; H, 8.1. Preparation of propenoxyoxetane Elbe hydroxygxetgnes of this1 dinvention can be reacted 10 W1 organic p osp ites o yie oxetane ring-containing Allyloxyoxetane (456 g.) and 700 g. of drmethylsulfoxhosphites which are useful as stabilizers for halogenwefaPlaced m a three'nficked flask containing resins. For example, 2 moles of the compound: with stirring, 51 g. of potassium t-butoxide was added at room temperature over a 5-10 minute period. An exothermic reaction occurred with the temperature rising to CH2CH-CH2 a maximum of 45-55 C. after 30 minutes. After alloW- 5 ing the reaction mixture to cool for 30 minutes, examination of the mixture by near infrared indicated complete f i i z 2' mcffle of 2 i phosp hue by conversion of the allylox-yoxetane to propenoxyoxetane. 33 5 f 2;; E 2: 53 g 2 ours The crude reaction product was filtered and the filtrate 20 0 5 i of so th 1 t i g i f distilled through a 24 Goodloe column. A total of 388 f th f l e y a e 0 yle n'oxe y p g. of 3-propenoxyoxetane, B.P. 75 C. at 50 mm. Hg, p 1 e o e Ormu n 1.4426, (85 percent yield) of the formula: IZ/CE 0 CH ror1 oH2 25 \CH2 OCH=CHCH3 err, was recovered at 7377 C. under 50 mm. Hg. Analysis.-Calcd for C H O C, 63.0; H, 8.78. Found: c, 62.4; H, 8.89. Th h h (I) e p osp ite compounds of the type of (I), which are EXAMPLES ILHI particularly valuable as stabilizers for halogen-containing Two additional experiments were performed in the resins, can be employed in an amount of from about same manner as described in Example 1. Details relating 0.005 to about 15 percent, preferably from about 0.5 to to these two examples are given in the table below: 6 percent, by Weight of the resin. These phosphite sta- Allyloxyoxetane Potassium Propenoxyoxetane Dimethylt-butox- Yi ld Example G. Moles sultoxide, g. ide, g. G. Moles (percent) 11 864 7. s 1, 344 100 735 e. 35 III 1, 730 15. 2 2, (ass 220 1, 510 13. 2 87.5

EXAMPLE IV bilizers are especially useful when employed with halo- Preparation of hydroxyoxetane gen-containing vinyl and vinylidene resins in which the halogen is attached directly to the carbon atoms. For ex- 3-Pf0Pe110XY0Xetane 0146 111016) Was YP ample, vinyl chloride resins can be stabilized with matech rina d n a Water 80- 8') H1174 rials of this type as also can be resins composed of mixture at 0 0 in the pfesencfi of cacoa 8- tures of chlorinated polyethylene, polyvinyl chloride, etc. 0- H1016) as a hydrogen chlm'lde f The f These stabilizers can be incorporated with the resin by tor was a 500 ml. flask equipped with stirrer, chlorine milling on r0118 at 100 to 6 or by any other f the p rg a Platinum Calomel Flecfrodes (atfached to methods well known in the art which provide for uniform P meter) for monitormg the oxldatlon f P ch10 r distribution of the compound added throughout the resin. fine Was introduced a Tale of about mllllmoles P"? Additional details on the use of phosphite stabilizers of minute for mlnutes- Chromatographlc analysls this type can be found in Hechenbleikner et al. US. Patshowed that the propenoxyoxetane had been completely mt 3,209,013, consumed. Two new peaks were observed; the first alpha- W112;E is claimed i chloropropionaldehyde eluting just after water and, the L A compound f the f la; second being a higher boiling component having a retention time slightly greater than that of glycidol. The latter peak was identified as hydroxyoxetane by infrared and HzCCH-CH2 nuclear magnetic resonance studies. After the reaction 0 R mixture had been filtered, the filtrate was saturated with l E sodium chloride and then extracted six times with 200 CHTCH H ml. portions of methyl ethyl ketone and twice with 50 ml.

portions of butanol. The combined extracts were dried over anhydrous magnesium sulfate and the solvents removed under atmospheric pressure (max. head temperature 81 C.). Distillation of the concentrated residue under reduced pressure yielded a main fraction of 3-hydroxyoxetane, 6.6 g., at 80 C./l0 mm. Hg. Chromatographic analysis of all fractions as well as of the flask residue indicated a yield of about 70 percent of 3-hydroxyoxetane. Redistillation of the main fraction gave wherein R and R are each selected from the group consisting of hydrogen and alkyl of from 1 to 5 carbon atoms.

2. The compound:

(References on following page) References Cited UNITED STATES PATENTS FOREIGN PATENTS 2/1965 Great Britain.

OTHER REFERENCES JACS, 81, July 5, 1959, PP. 3374-3379. JACS, 78, July 20, 1956, pp. 3432-6. Journal of the American Chemical Society, vol. 83

5 Apr. 5, 1961, p. 1173.

NORMA S. MILESTONE, Primary Examiner.

US. Cl. X.R. 

